Hair dressing composition



A ate i This invention relates to an aqueous-alcohol hair dressingcomposition containing a water soluble silicone and a water solublelower alkoxy polyoxyalkylene glycol or polyoxyalkylene diol.

Aqueous-alcohol hair dressing compositions containing lower alkoxypolyoxyalkylene glycols as hair grooming agents are known but suchcompositions are lacking in that they groom the hair well but do notprovide luster to the hair which has heretofore been obtained withgreasy hair dressings such as those made from mineral oil. (Greasy hairdressings have the disadvantages of staining pillows, furniture, hatbands etc. and of being diificult to wash from the hair andhands.)Moreover, aqueousalcohol hair dressing compositions containing the usuallower alkoxy polyoxyalkylene glycols require additives to preventseparation at lower temperatures.

It is an object of this invention to provide an aqueous alcoholic hairdressing composition which has excellent grooming properties and whichwill produce an outstanding luster to the hair without greasiness.

It is another object of this invention to provide an aqueous alcoholichair dressing composition which is clear, and transparent, which can bewashed from the comb and hands with water and which does not separateeven under extreme cooling.

It was found that these and other objects are achieved in anaqueous-alcohol hair dressing containing a particular water solublesiloxane oxyalkylene block copolyrner as a luster imparting agent and aparticular type of Water soluble lower alkoxy polyoxyalkylene glycol orpolyoxyalkylene diol as a grooming agent which will not separate at lowtemperatures and which does not require the use of a separationprevention additive.

The water soluble siloxane oxyalkylene block copolymers used as a lusterimparting agent in the composition of the present invention have thegeneral formula ((0113) ZSiO)D( nH2nO) 104 9 ogrusi or ona)isio) o..nzno.cirn

O(kCH3)2Sl.O)i-( n 2nO) 2 4 0 where the average values of p, q and r areeach about 6 and z is an integer of about 30 and the (C H O) unit is amixed polyoxyethyleneoxypropylene block containing an average of about17 oxyethylene units and 13 oxypropylene units. These silicones aredescribed in detail in US. Patent 2,834,748 issued to D. L. Bailey andF. M. OConner. They are completely soluble in the waterethanol mixturesand compatible with the hair grooming agent in the compositions of thepresent invention. They are non-greasy when applied to the hair. Theyprovide a luster on the hair at least equal to the luster provided bymineral oil hair dressing preparations. Surprisingly it was found thatif the luster imparted to the hair by the siliconecontainingcompositions of this invention fades after a period oftime, the lusteris'immediately restored upon ordinary combing or brushing. The siliconecompounds which are customarily used in cosmetics are water insoluble.The use of such insoluble silicones in hair dressing compositions wouldresult in a product which would be difficult to wash off the hands andhair and which would be diflicult to make clear and homogeneous. Suchinsoluble silicones might be emulsified, but emulsifiers would causefoaming of the hair dressing which is undesirable. The above describedsi-loxane oxyalkylene block copolymers appear to be unique in thesolubility, compatibility and luster-imparting qualities which make themoutstanding ingredients in the hair dressing compositions of thisinvention.

The hair dressing should contain about 0.3% to about 15% of thesiloxane-oxyalkylene block copolymer luster imparting agent. (Allpercentages, parts and ratios used herein are by weight.) If less thanabout 0.3% is used the luster eflect is not apparent. If more than about15% is used there is no noticeable increase in luster. 0.5% to 2% ispreferred.

The grooming agent used in the hair dressing compositions of thisinvention is a Water soluble lower alkoxy polyoxyalkylene glycol orpolyoxyalkylene diol in which the oxyalkylene is a mixture ofoxyethylene and oxypropylene in a ratio of about 3:1 to about 1:3 andwhich have an average molecular weight greater than about 900 and notgreater than about 4000. Lower alkoxy is intended to include alkoxyradicals ranging in carbon atom content from 1 to about 6.Polyoxyethyleneoxypropylene diols are described in US. Patent 2,425,845issued to Toussaints et al. The butoxy polyoxyalkylene glycols havingthe oxyalkylene characteristics described above are the preferredgrooming agents in the compositions of the present invention,particularly wherein the oxyethylene and oxypropylene are in about equalparts by weight. However, other alkoxy polyoxyalkylene glycols can beused; for example, methoxy, ethoxy, propoxy, pentoxy and hexoxypolyoxyethyleneoxypropylene glycols, wherein the ratio of oxyethylene tooxypropylene is in the range of 3 :1 to 1:3, are excellent as hairgrooming agents in the compositions described herein.

The above-described hair grooming agent is highly satisfactory in a hairdressing composition. Its oily characteristics impart groomingproperties to the composition, but the agent is water soluble andtherefore does not have the undesirable greasy properties of the usualhair oils such as mineral oil. Moreover, being water soluble, it can beeasily combined with water (which has desirable hair setting properties)without the need for emulsifying agents. Furthermore, as mentionedabove, no separation-prevention additives have to be used with the hairgrooming agent to maintain a clear, homogeneous composition. This isattributable to the above-specified balance of oxyethylene andoxypropylene, i.e. the 1:3 to 3:1 ratio range.

The hair dressing should contain about 10% to about 55% of the hairgrooming agent, i.e. the 'alkoxy polyoxyalkylene glycol orpolyoxyalkylene diol as described above. If less than about 10% is used,the hair grooming effect is not lasting or satisfactory. No more thanabout 55% is used in order to permit the inclusion of water and ethanolin sufficient amounts to provide a clear, fluid, homogeneous product.20% to 30% is the preferred amount of hair grooming agent. The hairgroom agent and luster imparting agent should not total more than about60% of the composition. i

Ethanol is used with water in the solvent portion of the compositions ofthis invention. Ethanol is preferred over other solvents because it doesnot involve the toxicity problems of methanol or the odor problems ofisopropanol or the evaporation problems of the higher alcohols. Pureethanol or ethanol containing the usual denaturants can be used; thebitter denaturants are preferred over methanol as a denaturant.

The hair dressing composition of this invention should contain fromabout 25% to about 70% water. At least about 25% water is necessary toprovide, with the ethanol, a fluid vehicle for the hair dressing and toprovide a hair setting action. About 70% water is the most that can beused and still permit the inclusion of ethan01, the hair grooming agentand the luster imparting agent. 25% to 50% water is preferred.

The hair dressing composition should contain from about to about 60%ethanol. At least about 10% ethanol is necessary to inhibit hydrolysisof the siloxaneoxyalkylene block copolymer luster imparting agent in thecomposition. This block copolymer tends to break down after a time ifused solely with water or when the ethanol content of the hair dressingis less than about 10%. Also at least about 10% ethanol is necessary toprovide a non-greasy feel to the hair dressing because of its tendencyto reduce viscosity and surface tension. Ethanol is also useful todissolve any perfume oils used in the hair dressing thereby insuring aclear product. Ethanol also acts to reduce any undesirable sudsingtendency of the dressing. Ethanol is a useful constituent (I the hairdressing since it evaporates rapidly after application, giving acooling, tingling sensation to the scalp. Ethanol also has usefulantiseptic properties. Not more than about 60% ethanol should be used inorder to permit the inclusion of water, hair grooming agent and lusterimparting agent. 20% to 50% ethanol is preferred.

Various minor ingredients can be added to the composition of thisinvention to make it more attractive in appearance or use, but are notnecessary. Examples of such minor ingredients are: up to about 1% color(in up to about 1% solution); up to about 5% of a thickening agent suchas methyl cellulose, hydroxypropylmethyl cellulose or sodiumcarboxymethyl cellulose; up to about 2% perfume; up to about 0.1% ofantifoa-ming agents such as silicone foam depressants. From about 0.1%to about 5% of a germicidal agent, such as dodecyl or cetyl dimethylbenzyl ammonium chloride or benzethonium chloride, is a very desirableadditive to the hair dressing. Such germicidal agents can be buffered ifdesired.

The hair dressing composition of this invention is illustrated by thefollowing examples.

EXAMPLE I A hair dressing composition was obtained by uniformly mixingtogether the following ingredients:

24.0 parts butoxypolyoxyethyleneoxypropylene glycol having a molecularweight of 1200 and a viscosity of 400 Saybolt Universal seconds at 100F. wherein the oxyethylene and oxypropylene are in equal parts 1.0 partmixture of siloxane-oxyalkylene block copolymers having the generalformula where the average values of p, q and r are each 6, z is 30 andthe (C H O) unit is a mixed polyoxyethyleneoxypropylene block containingan average of 17 oxyethylene units and 13 oxypropylene units.

0.2 part perfume 0.01 part Antifoam B (Dow-Corning silicone foamdepressant) 45.0 parts ethanol 27.73 parts water .06 part color (1%aqueous solution) The hair dressing was a clear, transparent andhomogeneous fluid. It showed no tendency to separate or become cloudyeven after long shelf-life tests or after being cooled to temperaturesas low as 0 F.

When the hair dressing was worked into human hair' (male subject),excellent grooming of the hair was ob-' tained when it was combed orbrushed. There was no greasiness. The hair dressing was Washed from thecomb and hands easily with plain water.

When the hair was combed after application of the dressing, it had anoutstanding luster. The luster was at least equal to the luster obtainedby using a greasy, mineral oil hair dressing. The luster was superior toa hair dressing composition as set forth in this example which omittedthe siloxane oxyalkylene block copolymer, and superior to hair withoutdressing or with other dressings as set forth in Table I below.

The procedure for measuring luster utilizes a recording goniophotometer,the principles of which are described in an article by R. S. Hunter,entitled Gloss Evaluation of Materials, ASTM Bulletin No. 186, December1952, page 48.

The following procedure was used when measuring the luster of hair:

(1) A 5 gram switch of hair was prepared without thinning the ends. Itwas then Washed in a shampoo anddried.

(2) The luster of the clean hair without dressing was measured with thegoniophotorneter.

(3) 0.2 gram of hair dressing was applied to the hair with aneyedropper. The hair switch was then combed for 30 seconds. Combing' Wasdone in only on direction, alternating the sides of the switch.

(4) The luster of the switch was measured with the goniophotometer 30seconds after combing was stopped.

The following results were obtained with six switches of hair, eachswitch having the same characteristics and each switch being tested asnoted above. The same procedure was used with each switch that wastreated with hair dressing.

Table I Hair Dressing: Luster value Composition of ExampleI 88Composition of Example I without the siloxane oxyalkylene blockcopolymer 77.5 Mineral oil 87 Ethanol 76 Hair dressing containing 70%ethanol, 18%

butoxy polyoxypropylene glycol and the remainder water 76 Clean switchwithout dressing 77.5

/2% benzethonium chloride, a cationic germicide, was added to thecomposition of Example I without affecting its physical or hair dressingcharacteristics. 'However, it provided the hair dressing with aneffective germicidal action. 2% buffered dodecyl or cetyl dime thylbenzyl ammonium chloride can also be used as a germicidal agent.

The following hair grooming agents can be substituted in equal amountsfor the butoxy polyoxyethyleneoxypropylene glycol in Example I withsubstantially equal results:

Butoxy polyoxyethyleneoxypropylene glycol having a molecular Weight of2650 and a viscosity of 2000 Saybolt Universal seconds at F., whereinthe oxyethylene and oxypropylene are in equal parts;

Polyoxyethyleneoxypropylene diol having a molecular weight of 990 and aviscosity of 450 Saybolt Universal seconds at 100 F wherein the ratio ofoxyethylene to oxypropylene is 3:1.

EXAMPLE n Hair dressing compositions having characteristicssubstantially equivalent to those of the composition in Ex ample I wereobtained by uniformly mixing the following ingredients in theproportions indicated respectively for the different compositions.

Compositions A and D, because of their high water content had slightlybetter hair setting properties than the composition of Example I.Composition A, wherein the water is about 45 parts, and additionallycontains about 2 par-ts of a germicidal agent, is the preferred hairdressing composition of this invention.

Composition D, because of the presence of hydroxypropyl methyl cellulosewas a homogeneous, clear, very viscous fluid, having a viscosity of50,000 cp. at 80 F. It is especially useful for being dispensed from asoft metal or plastic tube.

What is claimed is:

1. A clear fluid homogeneous hair dressing composition consistingessentially of (a) as a hair grooming agent from about to about 55% of acompound selected from the group consisting of water soluble loweralkoxy polyoxyalkylene glycols and polyoxyalkylene di- 01s, theoxyalkylene in said compound being a mixture of oxyethylene andoxypropylene in a weight ratio of about 3 :1 to about 1:3, and theaverage molecular weight of said compound being greater than about 900and not greater than about 4000; (b) as a luster imparting agent fromabout 0.3% to about water soluble siloxane oxyalkylene block copolymershaving the general formula wherein the average values of p, q and r areeach about 6, z is an integer of about 30 and the (C H O) unit is amixed polyoxyethyleneoxypropylene block containing an average of about17 oxyethylene units and 13 oxypropylene units; (c) from about 20% toabout 60% ethanol; (d) from about to about 70% water; all percentagesbeing by weight; the total percent of ingredient (a) and ingredient (b)being not greater than about 60%.

2. A clear fluid homogeneous hair dressing composition consistingessentially of (a) as a hair grooming agent from 20% to 30% of acompound selected from the group consisting of water soluble loweralkoxy polyoxyalkylene glycols and polyoxyalkylene diols, theoXyalk-ylene in said compound being a mixture of oxyethylene andoxypropylene in a weight ratio of about 3:1 to about 1:3, and theaverage molecular weight of said compound being greater than about 900and not greater than about 4000; (b) as a luster imparting agent from0.5% to 2% water soluble siloxane oxyalkylene block copolymers havingthe general formula wherein the average values of p, q and r are eachabout 6, z is an integer of about 30 and the (C H o) unit is a mixedpolyoxyethyleneoxypropylene block containing an average of about 17oxyethylene units and 13 oxypropylene units; (c) from 20% to ethanol;(d) from 25% to 50% water; all percentages being by weight.

3. The composition of claim 2 wherein ingredient (a) comprises butoxypolyoxyethyleneoxypropylene glycol having a molecular weight of about1200 and the oxyethylene and oxypropylene are in about equal parts byweight and which contains from about 0.1% to about 5% of a quaternaryammonium germicidal agent.

4. A clear homogeneous hair dressing composition consisting essentiallyof about 1 part water soluble siloxane oxyalkylene block copolymershaving the general formula 0 B)2S 0)p(Gn 2nO) zC H C2H5Si-O ((CHa) zsio)q(C n ZnO) 1 4 0 O((OH3)ZSiO)r(OnHflnO) 1104119 wherein the averagevalues of p, q and r are each about 6, z is an integer of about 30 andthe (C H O) unit is a mixed polyoxyethyleneoxypropylene block containingan average of about 17 oxyethylene units and 13 propylene units, about24 parts butoxy polyoxyethyleneoxypropylene glycol having a molecularweight of about 1200 and wherein the oxyethylene and oxypropylene are inabout equal parts, about 45 parts water, about 28 parts ethanol andabout 2 parts quaternary ammonium germicidal agent, all parts being byweight.

References Cited in the file of this patent UNITED STATES PATENTS2,771,394 Mehafr'ey Nov. 20, 1956 2,825,693 Beaubien et a1 4, 19582,834,748 Bailey et al. May 13, 1958 2,917,480 Bailey et al. Dec. 15,1959 :UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,061,519 October 30, 1962 David de L. Rosekrans It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 3, line 30, for ."0" read of column 6, line 35, for "C4110" read11113.40, for ."propylene'fv read oxypropylene Signed and sealed this9th day of April 1963 (SEAL) Attest:

ESTON G. JOHNSON Attesting Officer DAVID L. LADD Commissioner of Patents

1.A CLEAR FLUID HOMOGENEOUS HAIR DRESSING COMPOSI-TION CONSISTINGESSENTIALLY OF (A) AS A HAIR GROOMINGG AGENT FROM ABOUT 10% TO ABOUT 55%OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF WATER SOLUBLE LOWERALKOXY POLYOXALKYLENE GLYCOLS AND POLYOXYALKYLENE DI-E OLS, THEOXYALKYLENE IN SAID COMPOUND BEING A MIXTURE OF OXYETHYLENE ANDOXYPROPYLENE IN A WEIGHT RATIO OF ABOUT 3:1 TO ABOUT 1:3, AND THEAVERAGE MOLECULAR WEIGHT OF SAID COMPOUND BEING GREATER THAN ABOUT 900AND NOT GREATER THAN ABOUT 4000; (B) AS A LUSTER IMPARTING AGENT FROMABOUT 0.3% TO ABOUT 15% WATER SOLUBLE SILOXANE OXYALKYLENE BLOCKCOPLYMERS HAVING THE GENERAL FORMULA